Observations Less than the Analytical Limit of Detection: A New Approach

Abstract

Solutions are given for plume rise assuming a power-law wind speed profile in a stably stratified layer for point and finite sources with initial vertical momentum and buoyancy. For a constant wind speed, these solutions simplify to the conventional plume rise equations in a stable atmosphere. In a shear layer, the point of maximum rise occurs further downwind and is slightly lower compared with the plume rise with a constant wind speed equal to the wind speed at the top of the stack. If the predictions with shear are compared with predictions for an equivalent average wind speed over the depth of the plume, the plume rise with shear is higher than plume rise with an equivalent average wind speed.     

Penetration and Duration of Oxidant Air Pollution in the South Coast Air Basin of California

On June 18, 19, and 20, 1970, two aircraft, a rawinsonde, two pibal stations, and four ground stations provided simultaneous samples of total oxidant, temperature, and winds up to 8000 ft in an area extending from Santa Monica, Calif., east to Redlands and north across the San Bernardino Mountains. It was shown that photochemical oxidant formed in the marine layer is vented up the slopes and over the crest of the San Bernardino Mountains during the day. Layers of high oxidant concentrations were detected above the inversion base, suggesting that some pollution is vented up the slopes and subsequently advected back to the south. The diurnal changes in the temperature inversion also contribute to the high concentration found above the inversion base. These processes result in multi-layers of pollution. The study suggests that oxidant air pollution is transported up to 80 mi to forested mountains, where severe damage to conifer species has been documented.     

The Nature and Sources of Haze in the Shenandoah Valley/Blue Ridge Mountains Area

In order to investigate the nature and sources of regional haze, the General Motors mobile Atmospheric Research Laboratory was used in the summer of 1980 to monitor ambient air quality in the Shenandoah Valley of northern Virginia. On the average, 92% of the total light extinction was due to scattering by particles; the remainder was due to scattering by gases and absorption by gases and particles. Sulfate aerosols were the most Important visibility-reducing species. Averaging 55% of the fine participate mass, sulfates (and associated water) accounted for 78% of the total light extinction. The second most abundant fine particulate, accounting for 29% of the fine mass, was carbon—most of which was organic. Most of the remaining particulate mass and extinction were due to crustal materials. It is estimated that 78–86% of the total light extinction was caused by anthropogenic aerosol, most of which originated in major source areas of the midwest.     

Airborne Emissions of Mercury from Municipal Solid Waste. I: New Measurements from Six Operating Landfills in Florida

Abstract

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg⁰) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from ～1–10 ng m^?2 hr^?1 over aged landfill cover, from ～8–20 mg/hr from LFG flares (LFG included Hg⁰ at μg/m³ concentrations), and from ～200–400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10–50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.     

Real-World Emissions from a Modern Production Vehicle Driven in Los Angeles

The emissions of hydrocarbons, nitric oxide, and carbon monoxide from one modern vehicle were measured using on-board instrumentation during about 350 miles of driving in Los Angeles, California. Emissions during on-road driving were compared to those obtained on dynamometers using the urban dynamometer driving schedule (UDDS). Although this study only used one driver and vehicle, tested over a relatively short distance, the analysis technique may be useful for a larger evaluation of off-cycle emissions.

The test vehicle had low warmed-up running emissions over the UDDS and for most of the on-road testing where the air-to-fuel ratio was maintained at the stoichiometric point. However, occasional heavily-loaded conditions during the on-road testing led to richerthan-stoiehiometric operation.

During these brief enrichment events, which lasted up to 29 seconds, CO emissions were increased by a factor of 2500 and HC by a factor of 40 over closed-loop stoichiometric operation. Nitrogen oxide emissions were similar during low-load stoichiometric operation and high-load enriched operation. The relatively constant gram-per-second emission rate of CO and HC observed during enriched operation suggests that such information can be combined with determinations of the frequency of enrichment for a large number of vehicles with similar calibrations to estimate the impact of the additional emissions from enrichment on emissions inventories.     

Arsenic and chromium speciation in an urban contaminated soil

The distribution and speciation of As and Cr in a contaminated soil were studied by synchrotron-based X-ray microfluorescence (μ-XRF), microfocused X-ray absorption spectroscopy (μ-XAS), and bulk extended X-ray absorption fine structure spectroscopy (EXAFS). The soil was taken from a park in Wilmington, DE, which had been an important center for the leather tanning industry along the Atlantic seaboard of the United States, until the early 20th century. Soil concentrations of As, Cr, and Pb measured at certain locations in the park greatly exceeded the background levels of these heavy metals in the State of Delaware. Results show that Cr(III) and As(V) species are mainly present in the soil, with insignificant amounts of Cr(VI) and As(III). Micro-XRF maps show that Cr and Fe are distributed together in regions where their concentrations are diffuse, and at local spots where their concentrations are high. Iron oxides, which can reduce Cr(VI) to Cr(III), are present at some of these hot spots where Cr and Fe are highly concentrated. Arsenic is mainly associated with Al in the soil, and to a minor extent with Fe. Arsenate may be sorbed to aluminum oxides, which might have transformed after a long period of time into an As-Al precipitate phase, having a structure and chemical composition similar to mansfieldite (AlAsO(4)?2H(2)O). The latter hypothesis is supported by the fact that only a small amount of As present in the soil was desorbed using the characteristic toxicity leaching procedure tests. This suggests that As is immobilized in the soil.     

Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States

Although the use of the insecticide γ-hexachlorocyclohexane (HCH) is now prohibited in many countries because of its hazardousness, stockpiles of γ-HCH still exist. In this study, we subjected γ-HCH to mechanochemical (MC) treatment with a planetary ball mill in the presence of CaO to investigate the feasibility of using this method for the treatment of γ-HCH stockpiles. We confirmed the degradation of γ-HCH and investigated the degradation mechanism. The major intermediates were identified to be 1,3,4,5,6-pentachlorocyclohexene (γ-PCCH) and chlorobenzenes (CBzs). Analysis of the steric structure of γ-HCH and identification of the degradation intermediates suggested that successive dehydrochlorination led to the formation of trichlorobenzenes. Products of further degradation (dichlorobenzenes, monochlorobenzene, and benzene) were also detected. Surprisingly, methane and ethane were also detected, which suggests cleavage of the C-C bonds of the cyclohexane ring and hydrogenation. All of the chlorine atoms in the γ-HCH could be transformed into inorganic chloride compounds by the MC treatment with CaO. Our results indicate that γ-HCH can be completely dechlorinated by MC treatment.     

Direct comparison of 210Po, 234Th and POC particle-size distributions and export fluxes at the Bermuda Atlantic Time-series Study (BATS) site

Particle-reactive, naturally occurring radionuclides are useful tracers of the sinking flux of organic matter from the surface to the deep ocean. Since the Joint Global Ocean Flux Study (JGOFS) began in 1987, the disequilibrium between ²³⁴Th and its parent ²³⁸U has become widely used as a technique to measure particle export fluxes from surface ocean waters. Another radionuclide pair, ²¹⁰Po and ²¹⁰Pb, can be used for the same purpose but has not been as widely adopted due to difficulty with accurately constraining the ²¹⁰Po/²¹⁰Pb radiochemical balance in the ocean and because of the more time-consuming radiochemical procedures. Direct comparison of particle flux estimated in different ocean regions using these short-lived radionuclides is important in evaluating their utility and accuracy as tracers of particle flux. In this paper, we present paired ²³⁴Th/²³⁸U and ²¹⁰Po/²¹⁰Pb data from oligotrophic surface waters of the subtropical Northwest Atlantic and discuss their advantages and limitations. Vertical profiles of total and particle size-fractionated ²¹⁰Po and ²³⁴Th activities, together with particulate organic carbon (POC) concentrations, were measured during three seasons at the Bermuda Atlantic Time-series Study (BATS) site. Both ²¹⁰Po and ²³⁴Th reasonably predict sinking POC flux caught in sediment traps, and each tracer provides unique information about the magnitude and efficiency of the ocean's biological pump.     

Multi-decadal changes in tundra environments and ecosystems: synthesis of the International Polar Year-Back to the Future project (IPY-BTF)

Understanding the responses of tundra systems to global change has global implications. Most tundra regions lack sustained environmental monitoring and one of the only ways to document multi-decadal change is to resample historic research sites. The International Polar Year (IPY) provided a unique opportunity for such research through the Back to the Future (BTF) project (IPY project #512). This article synthesizes the results from 13 papers within this Ambio Special Issue. Abiotic changes include glacial recession in the Altai Mountains, Russia; increased snow depth and hardness, permafrost warming, and increased growing season length in sub-arctic Sweden; drying of ponds in Greenland; increased nutrient availability in Alaskan tundra ponds, and warming at most locations studied. Biotic changes ranged from relatively minor plant community change at two sites in Greenland to moderate change in the Yukon, and to dramatic increases in shrub and tree density on Herschel Island, and in subarctic Sweden. The population of geese tripled at one site in northeast Greenland where biomass in non-grazed plots doubled. A model parameterized using results from a BTF study forecasts substantial declines in all snowbeds and increases in shrub tundra on Niwot Ridge, Colorado over the next century. In general, results support and provide improved capacities for validating experimental manipulation, remote sensing, and modeling studies.